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The stimulated emission at 722.9nm is observed by a direct photodissociation of the PbI2 molecules with a 266nm pulse laser. The possible dissociation channels are discussed. Two-photon resonant photodissociation mechanism is used to explain the generation of the 722.9 nm emission. The emission is measured at different incident laser energy and heat-pipe temperature. The obtained experimental result is well supported by the photodissociation mechanism given by us.